Substituted alkylphenols and method of producing the same



' Patented Now 13, 1934 I 1,980,966 PATENT OFFICE UNITED STATES SUBSTITUTED ALKYLPHENOLS AND METHOD OF PRODUCINGTHE SAME Frederick F. Blicke, 'Ann Arbor, Mich, assig'nor to Regents of the University of Michigan, Ann

Arbor, Micln, a corporation of Michigan No Drawing. Application February Serial N- 659,024

7 19 Claims. (on. 260-154) production of i-alkylphenols, having substituents,

It is known that i-alkylphenols are potent garmicides. It is also known that the introduction of such nuclear substituents as chlorine or bromine, augment the germicidal action of a phenol,

but, heretofore, no i-alkylphenol having such nuclear substituents as chlorine or bromine, has been made, which had a marked germicidal ct.- fect. My invention relates to the preparation of new products having in general a formula expressed as follows:

in which the substituent indicated by X" may be any one of the group including the halogens, CN, N02, and HgOH, andthe alkylradical, indicated by R" andhaving the general formula tion of a similar product, in which the substituents willbe in the 2, 6 positions, as indicated by the following formula:

I contemplate as within the scope of my invention 4-alkylphenols having a nuclear substituzs. 193a,

ent in the 2 position, or nuclear substituents in the 2,6 positions, or a mixture of such products.

Zincke; Schneider. and Emmerich (Ann., 328, 277

(1903)) have heretofore described. the produc tion of 2-chloro-4-methylphenol, but no germi cidal tests were conducted-by themon this substance. Tests have shown that it possesses a relatively low phenol coeiilcient and does not have marked germicidal powers.

m ssus-:0

My research hasshown that, in general, the

phenol coeflicient increases with the number of carbon atoms in the alkyl group and that, where the alkyl group has less than three carbon atoms, the phenol coemcient is low and the germicidal powers of the product are not marked. My invention, therefore, is restricted tosubstituted 4- alkylphenols containing more than two carbon atoms in the alkyl group, as these appear to be the products having marked germicidal powers. The alkyl group may be of the straight or of the branched chain type. V

I believe that substitution, in the 2 or 2,6 positions in the 4-alkylphenols containing more than two carbon atoms in the alkyl group, of any nuclear substituent, of the group including the halogens, CN, N02, and HgOH, will result in an increase in the phenol coeflicient and yield products having marked germicidal powers, but, at this time, I have not yet investigated the germicidal powers of any of these substitution products other thanthose in which the nuclear substituent is chlorine.

The following specific example illustrates one method by means of which I have obtained 2- 'chloro-i-n-heptylphenol: 48 g. of 4-n-heptylphen01 are mixed with 34 g. of sulfuryl chloride and after five days the material is distilled directly or it may first be washed free from halogen compounds with sodium bicarbonate solution and the chlorophenol purified by distillation. The product, 2-chloro-4-n-heptylphenol is ordinarily obtained as a liquid which is practically colorless, odorless and tasteless and which boils at 290-291 C. under about 738 mm. pressure. The solid alpha naphthoate produced from this compound melts at 45-47" C. The product, 2-chloro-4-n-heptylphenol, is of very low toxicity and has a phenol coemcient of about 666 measured by the Reddish method now oflicially recognized by the Food, Drug and'Insecticide Administration of the Department of Agriculture. 1

If the amount of sulfuryl-chloride used is increased, there will result a mixture of 2,6 dichloro- 4-n-heptylphenol and 2-chloro-4-n-heptylphenol. If the amount of sulfuryl chloride is increased to more than two molecular equivalents, that is, in the example given, is in excess of 68 g., the resulting product will be substantially all 2,6 dichloro- 4-n-heptylphenol. Other chlorinating agents or may be incorporated "mu or other suitable solvent.

chlorine itself may be used instead of sulfuryl chloride.

I have obtained 2-ch1oro-4-n-hexylphenol by the following method: 44 g. of 4-n-hexylphenol are mixed with 34 g. of sulfuryl chloride and after five days the material is washed with sodium bicarbonate solution and the 2-chloro-4-n-hexy1- phenol purified by distillation. The product is ordinarily obtained as a liquid, which is practically colorless, odorless and tasteless and boils at 275- 276 C. under about 140 mm. pressure. The solid alpha naphthoate produced from this compound melts at 43-45 C. The product, 2-chloro-4-nhexyiphenol, has a phenol coefllcient of about 444, measured by the Reddish method. It has very low toxicity.

In the following table, I have given the boiling points the melting points of the corresponding alpha napthoates, and the phenol coemcients (determined by the Reddish method) of the various 2 -chloro-4-n-alkylphenols, which I have investigated:

r i 2-ch1oro-4-n-clkylphenols Phenol I coefllclent Propy] rat-2x1 (741 mm.) 71-73 31 Butyl 243-244 (735 mm.) 44-46 115 :11 250-200 (740 mm 63-65 333 Buy] 275-276 (740 mm 43-45 444 Heptyl W291 (738 mm. -47 666 In comparison with the ioregoing, tests have shown that the phenol coeflicients of 2-chloro-4- 1 methylphenol and 2-chloro-4-ethylphenol are only-about 8.7 and 17.7, respectively.

The substituted alkylphenols of my invention with other medicaments, or may be used dissolved in dilute alcohol, dilute Furthermore, they may be used in the form of esters, ethers or salts. 1

'I aware that the products and methods described herein may be varied considerably without departing from the spirit of my invention, and, therefore, I claim my invention broadly as indicated by the appended claims.

What I claim is:

1. A new product consisting of a 4-,allwlphenol containing more than five carbon atoms in the alkyl group and halogen substituents in the 2, 6 positions. I

2. A new product consisting of\g-chloro4-nheptylphenol, said product being a practically colorless, tasteless and odorless liquid; boiling at about 290 C. under'a pressure of 738 mm. and having a phenol coeflicient exceeding $500.

[3. A new product consisting of 2chloro-4-n-' hexylphenol, said product being a practically colorless, tasteless and odorless liquid, boiling at about. 275 C. under a pressure of 740 mm. and

having a phenol coeificient exceeding 350.

ing a high phenol coefllcient comprising subjecting 4-n-heptylphenol to reaction with suliuryl chloride.

'l. The process 01' producing a compound having a high phenol coeflicient comprising mixing 4-n-heptylphenol and sulfuryl chloride; allowing the mixture to stand until the reaction is substantially\ effected and eliminating any rei maining sulfuryl chloride.

8. The process of producing a compound having a high phenol coefficient comprising mixing 4-n heptylphenol with from one to three molecular equivalents of suliuryl chloride, and allowing the mixture to stand until reaction is substantially effected.

9. The process of producing a compound having a high phenol coefiicient comprising subjecting 4-n-hexylphenol' to chloride.

10. The process of producing a compound having a high phenol coeilicient comprising mixing 4-n-hexylphenol with from one to three molecular equivalents of suifuryl chloride, and allowing the mixture to stand until reaction is sub-- stantially effected.

. FREDERICK F. BLICKE.

DI SCLAI M E R 1,980,966.Freder'ick F. Bl'icke, Ann Arbor, Mich. SUBSTITUTED ALKYLPHENOLB AND METHOD or PRODUCING THE SAME. Patent dated November 13, 1934.

Disclaimer filed October 29 1936 by the assi gnee Re ents 0 the Un ve t of Mwh'agan; the exclusive hcenee, Frederick Starn and lompanz $11 sentmg and concurring.

Hereb enters this disclaimer to claims 1, 4, and .5 in said specification.

Gazette November 24, 1986'] reaction with sulfuryl may be incorporated "mu or other suitable solvent.

chlorine itself may be used instead of sulfuryl chloride.

I have obtained 2-ch1oro-4-n-hexylphenol by the following method: 44 g. of 4-n-hexylphenol are mixed with 34 g. of sulfuryl chloride and after five days the material is washed with sodium bicarbonate solution and the 2-chloro-4-n-hexy1- phenol purified by distillation. The product is ordinarily obtained as a liquid, which is practically colorless, odorless and tasteless and boils at 275- 276 C. under about 140 mm. pressure. The solid alpha naphthoate produced from this compound melts at 43-45 C. The product, 2-chloro-4-nhexyiphenol, has a phenol coefllcient of about 444, measured by the Reddish method. It has very low toxicity.

In the following table, I have given the boiling points the melting points of the corresponding alpha napthoates, and the phenol coemcients (determined by the Reddish method) of the various 2 -chloro-4-n-alkylphenols, which I have investigated:

r i 2-ch1oro-4-n-clkylphenols Phenol I coefllclent Propy] rat-2x1 (741 mm.) 71-73 31 Butyl 243-244 (735 mm.) 44-46 115 :11 250-200 (740 mm 63-65 333 Buy] 275-276 (740 mm 43-45 444 Heptyl W291 (738 mm. -47 666 In comparison with the ioregoing, tests have shown that the phenol coeflicients of 2-chloro-4- 1 methylphenol and 2-chloro-4-ethylphenol are only-about 8.7 and 17.7, respectively.

The substituted alkylphenols of my invention with other medicaments, or may be used dissolved in dilute alcohol, dilute Furthermore, they may be used in the form of esters, ethers or salts. 1

'I aware that the products and methods described herein may be varied considerably without departing from the spirit of my invention, and, therefore, I claim my invention broadly as indicated by the appended claims.

What I claim is:

1. A new product consisting of a 4-,allwlphenol containing more than five carbon atoms in the alkyl group and halogen substituents in the 2, 6 positions. I

2. A new product consisting of\g-chloro4-nheptylphenol, said product being a practically colorless, tasteless and odorless liquid; boiling at about 290 C. under'a pressure of 738 mm. and having a phenol coeflicient exceeding $500.

[3. A new product consisting of 2chloro-4-n-' hexylphenol, said product being a practically colorless, tasteless and odorless liquid, boiling at about. 275 C. under a pressure of 740 mm. and

having a phenol coeificient exceeding 350.

ing a high phenol coefllcient comprising subjecting 4-n-heptylphenol to reaction with suliuryl chloride.

'l. The process 01' producing a compound having a high phenol coeflicient comprising mixing 4-n-heptylphenol and sulfuryl chloride; allowing the mixture to stand until the reaction is substantially\ effected and eliminating any rei maining sulfuryl chloride.

8. The process of producing a compound having a high phenol coefficient comprising mixing 4-n heptylphenol with from one to three molecular equivalents of suliuryl chloride, and allowing the mixture to stand until reaction is substantially effected.

9. The process of producing a compound having a high phenol coefiicient comprising subjecting 4-n-hexylphenol' to chloride.

10. The process of producing a compound having a high phenol coeilicient comprising mixing 4-n-hexylphenol with from one to three molecular equivalents of suifuryl chloride, and allowing the mixture to stand until reaction is sub-- stantially effected.

. FREDERICK F. BLICKE.

DI SCLAI M E R 1,980,966.Freder'ick F. Bl'icke, Ann Arbor, Mich. SUBSTITUTED ALKYLPHENOLB AND METHOD or PRODUCING THE SAME. Patent dated November 13, 1934.

Disclaimer filed October 29 1936 by the assi gnee Re ents 0 the Un ve t of Mwh'agan; the exclusive hcenee, Frederick Starn and lompanz $11 sentmg and concurring.

Hereb enters this disclaimer to claims 1, 4, and .5 in said specification.

Gazette November 24, 1986'] reaction with sulfuryl 

